Sprayed article and making method

ABSTRACT

A sprayed article is prepared by thermally spraying ceramic particles of rare earth oxide or fluoride or metal particles of W, Mo or Ta onto an outer or inner surface of a cylindrical carbon substrate to form a sprayed coating, and burning out the carbon substrate, thus leaving the ceramic or metal-base sprayed coating of cylindrical shape having a wall thickness of 0.5-5 mm.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No. 14/509,927filed on Oct. 8, 2014, which is this non-provisional application claimspriority under 35 U.S.C. § 119(a) on Patent Application No. 2013-211792filed in Japan on Oct. 9, 2013, the entire contents of which are herebyincorporated by reference.

TECHNICAL FIELD

This invention relates to ceramic or heat-resistant metal-base sprayedarticles of hollow cylinder or cup shape and a method for preparing thesame.

BACKGROUND ART

Cylindrical or cup (crucible) shape ceramic articles of rare earthoxides or fluorides are generally prepared by molding methods includingmold pressing, rubber pressing (or isostatic pressing), slip casting,and doctor blade methods. There is furnished rare earth oxide powder fora particular molding method. The powder is molded into ceramic compactsof cylindrical or cup shape by any molding methods. The compacts aresubjected to firing, sintering and working steps until they are finishedinto products of the predetermined size. Molded articles ofheat-resistant metals, typically tungsten (W) are similarly prepared.

However, where it is desired to produce thin-wall articles, especiallyhaving a thickness of up to 5 mm, the standard molding methods aredifficult to produce acceptable molded articles because cracking occursduring the molding step. One common solution to this problem involvesmolding compacts having a greater thickness so as to ensure higheryields of compact formation, firing and sintering the compacts, andgrinding or otherwise machining the compacts to a wall thickness of upto 5 mm.

This method, however, is disadvantageous in that as the final articlebecomes thinner in wall thickness or greater in volume, the methodrequires a more amount of source material and a longer time for productfinishing. Because of cracking and warpage during sintering, the yieldof overall manufacture is substantially reduced, resulting in anincreased cost. This is a problem in the manufacture of ceramic or metalarticles.

CITATION LIST

Patent Document 1: JP-A H10-204655

Patent Document 2: JP-A H06-033215

Patent Document 3: JP-A 2004-346374

Patent Document 4: JP-B H06-55477

Patent Document 5: JP-A 2008-285734 (US 20090324916)

DISCLOSURE OF INVENTION

An object of the invention is to provide a method of preparing a sprayedshaped article consisting of a sprayed coating in high yields whileminimizing a loss of source material; and a sprayed shaped article whichis useful as equipment members requiring inertness, heat resistance,abrasion resistance, corrosion resistance, plasma resistance andchemical resistance.

The inventors have found that a sprayed shaped article which experiencesminimal warpage or deformation despite thin wall is prepared bythermally spraying ceramic particles of rare earth oxide or fluoride ormetal particles of W, Mo or Ta onto a surface of a carbon substrate ofcylindrical or cup shape to form a sprayed coating, and burning out thecarbon substrate, thus leaving the sprayed coating of cylindrical or cupshape having a reduced thickness.

In one aspect, the invention provides a method for preparing a sprayedarticle, comprising the steps of:

providing a carbon substrate of cylindrical shape having outer and innercircumferential surfaces,

thermally spraying ceramic particles of a rare earth oxide and/or rareearth fluoride or metal particles of at least one type selected from W,Mo and Ta, onto the outer or inner circumferential surface of the carbonsubstrate to form a sprayed coating, and

combustion treating the coated substrate to burn out the carbonsubstrate, thus leaving the ceramic or metal-base sprayed coating ofcylindrical shape having a wall thickness of 0.5 to 5 mm.

In another aspect, the invention provides a method for preparing asprayed article, comprising the steps of:

providing a carbon substrate of cup shape having outer and innercircumferential surfaces and outer and inner bottom surfaces,

thermally spraying ceramic particles of a rare earth oxide and/or rareearth fluoride or metal particles of at least one type selected from W,Mo and Ta, onto the outer circumferential and bottom surfaces or innercircumferential and bottom surfaces of the carbon substrate to form asprayed coating, and

combustion treating the coated substrate to burn out the carbonsubstrate, thus leaving the ceramic or metal-base sprayed coating of cupshape having a wall thickness of 0.5 to 5 mm.

In a preferred embodiment, only the step of combustion treating thecoated substrate is sufficient to burn out the carbon substrate.

In a preferred embodiment, the method may further comprise the step ofmachining the carbon substrate to reduce its wall thickness prior to thecombustion treating step, and the step of combustion treating the coatedsubstrate is sufficient to burn out the remaining carbon substrate.

In a preferred embodiment, the step of combustion treating the coatedsubstrate includes heating the coated substrate at a temperature of 800°C. to 1,700° C. in an oxidizing atmosphere.

In a preferred embodiment, the method may further comprise the step ofroughening the surface of the carbon substrate to be sprayed, prior tothe spraying step.

In a preferred embodiment, the spraying step includes alternatelyspraying ceramic particles of different rare earth oxides, oralternately spraying ceramic particles of a rare earth oxide and ceramicparticles of a rare earth fluoride to form the sprayed coating.

In a further aspect, the invention provides a sprayed article consistingof a sprayed coating of cylindrical or cup shape comprising a rare earthoxide and/or rare earth fluoride ceramic material or at least one metalselected from W, Mo and Ta, and having a wall thickness of 0.5 to 5 mm.

In a preferred embodiment, the sprayed article is obtained by forming asprayed coating of ceramic particles of a rare earth oxide and/or rareearth fluoride or metal particles of at least one type selected from W,Mo and Ta on an outer or inner circumferential surface of a carbonsubstrate of cylindrical shape, and removing the carbon substratetherefrom, thus leaving the sprayed coating, the sprayed articleconsisting of the ceramic or metal-base sprayed coating of cylindricalshape having a wall thickness of 0.5 to 5 mm.

In a preferred embodiment, the sprayed article is obtained by forming asprayed coating of ceramic particles of a rare earth oxide and/or rareearth fluoride or metal particles of at least one type selected from W,Mo and Ta on outer circumferential and bottom surfaces or innercircumferential and bottom surfaces of a carbon substrate of cup shape,and removing the carbon substrate therefrom, thus leaving the sprayedcoating, the sprayed article consisting of the ceramic or metal-basesprayed coating of cup shape having a wall thickness of 0.5 to 5 mm.

The sprayed article is preferably made of the rare earth oxide and/orrare earth fluoride.

In a preferred embodiment, the sprayed coating comprises alternatelysprayed layers of different rare earth oxides, or alternately sprayedlayers of a rare earth oxide and a rare earth fluoride.

Also preferably, the sprayed article is made of at least one metalselected from W, Mo and Ta.

Advantageous Effects of Invention

According to the invention, a sprayed shaped article is prepared bythermally spraying ceramic particles or metal particles onto a carbonsubstrate of cylindrical or cup shape to form a sprayed coating, andburning out the carbon substrate. The sprayed article consisting of thesprayed coating of cylindrical or cup shape having a thin wall can beprepared easily without a need for molding, firing and sintering stepsinvolved in the conventional methods. The sprayed article is useful asmembers in a variety of applications requiring inertness, heatresistance, abrasion resistance, corrosion resistance, plasma resistanceand chemical resistance.

DESCRIPTION OF PREFERRED EMBODIMENTS

A first embodiment of the invention is a method for preparing a sprayedshaped article, comprising the steps of providing a carbon substrate ofcylindrical shape having outer and inner circumferential surfaces,thermally spraying ceramic particles of a rare earth oxide and/or rareearth fluoride or metal particles of at least one type selected from W,Mo and Ta, onto the outer or inner circumferential surface of the carbonsubstrate to form a sprayed coating, and combustion treating the coatedsubstrate to burn out the carbon substrate, thus leaving the ceramic ormetal-base sprayed coating of cylindrical shape having a wall thicknessof 0.5 to 5 mm, the sprayed article being the sprayed coating alone.

A second embodiment of the invention is a method for preparing a sprayedshaped article, comprising the steps of providing a carbon substrate ofcup shape having outer and inner circumferential surfaces and outer andinner bottom surfaces, thermally spraying ceramic particles of a rareearth oxide and/or rare earth fluoride or metal particles of at leastone type selected from W, Mo and Ta, onto the outer circumferential andbottom surfaces or inner circumferential and bottom surfaces of thecarbon substrate to form a sprayed coating, and combustion treating thecoated substrate to burn out the carbon substrate, thus leaving theceramic or metal-base sprayed coating of cup shape having a wallthickness of 0.5 to 5 mm, the sprayed article being the sprayed coatingalone.

Below the methods of the invention are described in detail.

First, there is furnished a carbon substrate of predetermined dimensionsand a source powder for thermal spraying.

The carbon substrate used herein corresponds to a mold used in thestandard ceramic molding step. It may be formed by any techniques suchas cold isostatic pressing (CIP), extrusion, molding, and compaction(typically, composite body obtained by compacting fibrous carbon). Ofthese, CIP carbon substrates are preferred.

The shape of the carbon substrate may be a hollow cylinder, i.e., roundpipe which is open at both ends or a cylindrical cup or crucible, i.e.,bottomed round pipe which is open at one end and has a bottom at theother end. Notably, the hollow cylinder has outer and innercircumferential surfaces, and the cylindrical cup has outer and innercircumferential surfaces and outer and inner bottom surfaces. When thecircumferential wall of the substrate is perforated with a plurality ofthrough-holes, a sprayed article of cylindrical or cup shape havingcorresponding through-holes in its circumferential wall can be prepared.

The dimensions of the carbon substrate are not particularly limited aslong as the substrate is amenable to thermal spraying. For example, thesubstrate preferably has an outer diameter of 100 to 1,000 mm, morepreferably 200 to 600 mm, and an inner diameter of 80 to 980 mm, morepreferably 180 to 580 mm. The thickness of the carbon substrate is adifference between the outer and inner radii. The carbon substrateshould preferably be thick enough to ensure that the substrate ishandled or supported during thermal spraying and has a sufficientrigidity to withstand stresses of sprayed coating, and thin enough toensure that the substrate is readily removed in the later combustionstep. Specifically, the thickness of the carbon substrate (orcircumferential wall) is preferably 3 to 20 mm, more preferably 5 to 15mm. In the case of cup shape, the thickness of the bottom is preferablyequal to the thickness of the circumferential wall.

The source powder for thermal spraying is ceramic particles comprising arare earth oxide and/or rare earth fluoride or metal particles of atleast one type selected from W, Mo and Ta.

The rare earth oxides and fluorides used herein include oxides andfluorides of yttrium (Y) and lanthanoids, specifically oxides andfluorides of elements selected from yttrium (Y) and rare earth elementshaving atomic number 57 to 71, which may be used alone or in admixture.The preferred rare earth oxides are oxides of Y and Er. The preferredrare earth fluorides are fluorides of Y and Er. Also a mixture of a rareearth oxide with an oxide of another metal, typically Group 3B metalelement is useful as well as a complex oxide of a rare earth oxide andan oxide of another metal, typically Group 3B metal element. Exemplaryof the Group 3B metal are B, Al, Ga, In, and Ti elements. Where amixture or complex oxide of a rare earth oxide and another metal oxideis used, the content of rare earth oxide is preferably 10% to 90% byweight, and more preferably 30% to 80% by weight based on the totalweight of rare earth and other metal oxides.

The metal is at least one metal selected from tungsten (W), molybdenum(Mo) and tantalum (Ta), and preferably W or Mo.

The source powder to be sprayed preferably has an average particle sizeof 3 to 70 μm, and more preferably 15 to 60 μm. The average particlesize as used herein is a D₅₀ value (non-variance) as determined by themicrotrack method.

In the method of the invention, the source powder is thermally sprayedonto the carbon substrate. Prior to the spraying, the carbon substrateis preferably surface treated or roughened by shot blasting or similartechnique. Preferably the surface of the carbon substrate is roughenedto such an extent as to improve the adhesion of sprayed coating thereto.

Once the carbon substrate is prepared, the source powder is sprayedthereon. The type of thermal spraying is not particularly limitedalthough plasma spraying is preferred. Under preferred thermal sprayingconditions, for example, a plasma gas of argon gas in admixture withhydrogen gas, a current flow of 500 amperes, and a power of 35 kW, asprayed coating is deposited on the carbon substrate to thepredetermined thickness.

The thickness of the sprayed coating, which eventually becomes the wallthickness of the sprayed article, is specifically up to 5 mm, preferablyup to 4 mm, more preferably up to 3.5 mm, and most preferably up to 2.5mm. The minimum thickness is preferably at least 0.5 mm, more preferablyat least 1.0 mm, from the standpoint of preventing the sprayed articlefrom being damaged during handling.

Thermal stresses arise in the sprayed coating from such factors as theshape (size, thickness, etc.) and surface state as shot blasted of thecarbon substrate, and the difference between physical properties(coefficient of thermal expansion, modulus, etc.) of the carbonsubstrate and the physical properties (coefficient of thermal expansion,modulus, etc.) of the sprayed coating. Particularly in the case of alarge size carbon substrate, if the physical properties, thickness andsurface state of the carbon substrate do not match with the sprayedcoating, the sprayed coating develops cracks when it stands alone afterremoval of the carbon substrate. Then the desired article of hollowcylinder or cup shape is not available. It is then preferred to selectparameters of the carbon substrate and spraying material appropriate soas to suppress the generation of thermal stresses.

Next, combustion treatment is carried out to burn out the carbonsubstrate, i.e., to remove the carbon substrate.

In this step, preferably only the combustion treatment is sufficient toremove the carbon substrate. Then, the carbon substrate can be removedwithout increasing the number of steps. Alternatively, the carbonsubstrate is machined to reduce its wall thickness before combustiontreatment is carried out to burn out the remaining carbon substrate.This reduces the time required until the carbon substrate is removed.

The combustion treatment to burn out the carbon substrate preferablyincludes heating the coated substrate at a temperature of 800° C. to1,700° C. in an oxidizing atmosphere. Specifically, the sprayedcoating-bearing carbon substrate is placed in an oxidizing atmospherefurnace where heat treatment is carried out by heating at a temperatureof 800° C. to 1,700° C. and holding the temperature for a certain time,typically 30 minutes to 5 hours, until the carbon substrate is burntout. If the heating temperature is below 800° C., burning of the carbonsubstrate may be insufficient. If the heating temperature exceeds 1,700°C., the sprayed coating may be degraded. The oxidizing atmosphere is anatmosphere containing oxidizing gas. For example, the furnace is filledwith a gas mixture of oxygen and an inert gas (e.g., Ar) having anoxygen partial pressure of at least 0.02 MPa.

In the step, the carbon substrate is burnt out, i.e., is eventuallyremoved, leaving the sprayed coating of hollow cylinder or cup shape andcarbon substrate residues. There is obtained the sprayed article ofhollow cylinder or cup shape that has utilized the carbon substrate asmold.

On the surface of the sprayed coating in contact with the carbonsubstrate, there may be left behind carbon substrate residues. Suchresidues may be removed by blasting, machining, chemical treatment,firing or the like.

After removal of the carbon substrate, the sprayed coating may besomewhat deformed (e.g., warped or distorted) due to thermal stresses.Such deformation can be avoided by carefully tailoring the shape of thecarbon substrate. Alternatively, such deformation can be corrected byadditional thermal spraying on the surface of the sprayed coating thathas been in contact with the carbon substrate until finishing to thedesired thickness.

By the method of the invention, there is obtained a ceramic ormetal-base thin-wall sprayed article, which consists of a sprayedcoating of hollow cylinder or cup shape whose thickness is unchangedfrom the thickness as sprayed. That is, a ceramic or metal shaped bodyhaving a wall thickness of up to 5 mm, which is susceptible to cracks orstrains during molding if molded by conventional techniques such as moldpressing, rubber pressing (isostatic pressing), slip casting, doctorblade and the like, can be readily prepared by forming a sprayed coatingof ceramic or metal particles on the outer or inner circumferentialsurface of a cylindrical shape carbon substrate or on the outercircumferential and bottom surfaces or inner circumferential and bottomsurfaces of a cup shape carbon substrate, and removing the carbonsubstrate from the sprayed coating, with the advantages of causingneither cracks nor distortion to the ceramic or metal shaped body andeliminating a need for machining operation to reduce the wall thickness.Specifically, the sprayed shaped body may have a wall thickness of up to5 mm, preferably up to 4 mm, more preferably up to 3.5 mm, and even morepreferably up to 2.5 mm. The minimum thickness is preferably at least0.5 mm, more preferably at least 1.0 mm from the aspect of preventingdamage by handling.

As a variant of the inventive method, a sprayed article of hollowcylinder or cup shape can be prepared by alternately thermally sprayingceramic particles of different rare earth oxides, or alternatelythermally spraying ceramic particles of a rare earth oxide and ceramicparticles of a rare earth fluoride to form a sprayed coating. Forexample, from a sprayed coating obtained by alternately depositing asprayed layer of yttrium oxide and a sprayed layer of erbium oxide, eachhaving a thickness of 200 μm, a shaped article of hollow cylinder shapehaving a wall thickness of about 3 mm can be prepared. Also, between thesprayed layers of rare earth oxide and/or fluoride, a sprayed layer ofanother metal or metal compound may intervene. A composite shapedarticle of rare earth oxide and/or fluoride, which cannot be prepared bystandard ceramic molding techniques, can be prepared. In the applicationrequiring high purity, a sprayed article of high purity can be preparedby taking suitable means, such as, furnishing a carbon substrate andsource powder of high purity, conducting thermal spraying in a cleanenvironment, and effecting post-treatment such as acid washing, alkaliwashing, organic solvent washing, heat treatment, or precision cleaning.

Depending on the intended application, the resulting sprayed shapedarticle of cylinder or cup shape may be used as such or machined priorto use. Namely, the sprayed article may be machined, for example, bycutting, drilling, grinding, polishing or mirror polishing, whereby itis finished to the desired shape and surface state so that it is readyfor use.

The sprayed article manufactured by the invention is advantageously usedas members in a variety of applications where non-reactivity, heatresistance, abrasion resistance, corrosion resistance, plasmaresistance, and/or chemical resistance are required, for example,members (which must be plasma resistant) in semiconductor deviceprocessing chambers, laminate members having an electrode pattern oftungsten or the like formed therein and capable of producing anelectrostatic force such as members in electrostatic chucks, and settersused in sintering of magnet alloys.

EXAMPLE

Examples of the invention are given below by way of illustration, butnot by way of limitation.

Example 1

There was furnished a hollow carbon cylinder (CIP carbon substrate)having an outer diameter (OD) of 300 mm, an inner diameter (ID) of 294mm, and a height (H) of 100 mm. The outer circumferential surface of thecylinder was roughened by shot blasting. Using a source powder of Y₂O₃and a plasma gas of argon having hydrogen added thereto (argon/hydrogengas), plasma spraying was carried out on the roughened surface. Asprayed Y₂O₃ coating was deposited on the outer circumferential surfaceof the carbon cylinder. Plasma spraying was terminated when the coatingreached a thickness of 2 mm.

The Y₂O₃-coated carbon cylinder was placed in an oxidizing atmospherefurnace, where it was heated at 800° C. to burn out the carbon cylinder.With the furnace returned to room temperature, there was obtained ahollow cylindrical sprayed Y₂O₃ body having an OD of 305 mm, an ID of301 mm, a height of 100 mm and a wall thickness of 2 mm, that is, Y₂O₃ceramic cylinder from which the carbon cylinder had been removed(Example 1-1).

Using a 3D measuring instrument (model RVA1000A, Tokyo Seimitsu Co.,Ltd.), the Y₂O₃ ceramic cylinder of Example 1-1 was measured for OD, IDand roundness. With respect to the measuring positions, “top”, “middle”and “bottom” positions correspond to the upper end, center (in heightdirection) and lower end of the upright standing cylinder, respectively.Roundness was determined by the least squares center (LSC) method.Notably, the same measurements apply hereinafter. The results are shownin Table 1.

Next, an attempt was made to improve the roundness of the Y₂O₃ ceramiccylinder of Example 1-1. Namely, on the inner circumferential surface ofthe ceramic cylinder, a coating (sprayed Y₂O₃ coating of 1 mm thick) wasdeposited by plasma spraying under the same conditions as above. Thedual-sprayed Y₂O₃ body of cylindrical shape (Y₂O₃ ceramic cylinder) hadan OD of 305 mm, an ID of 299 mm, and a height of 100 mm (Example 1-2).

Using the 3D measuring instrument, the Y₂O₃ ceramic cylinder of Example1-2 was measured for OD, ID and roundness. The results are shown inTable 1. By additional thermal spraying on the inner surface, theceramic cylinder was improved in roundness.

TABLE 1 Measuring Diameter (mm) Roundness (mm) Cylinder position ID ODID OD Example top 301.08 305.73 2.228 2.237 1-1 center 301.12 305.842.175 2.169 bottom 301.17 305.83 2.125 2.170 Example top 299.15 305.800.162 0.201 1-2 center 299.10 305.79 0.194 0.154 bottom 299.17 305.810.250 0.178

Example 2

There was furnished a carbon crucible (carbon cup or CIP carbonsubstrate) having an OD of 300 mm, an ID of 294 mm, and a height of 100mm. The outer circumferential and bottom surfaces of the crucible wereroughened by shot blasting. Using a source powder of Y₂O₃ andargon/hydrogen gas, plasma spraying was carried out on the roughenedsurface. A sprayed Y₂O₃ coating was deposited on the outercircumferential and bottom surfaces of the carbon crucible. Plasmaspraying was terminated when the coating reached a thickness of 2 mm.

The Y₂O₃-coated carbon crucible was placed in an oxidizing atmospherefurnace, where it was heated at 800° C. to burn out the carbon crucible.With the furnace returned to room temperature, there was obtained acup-shape sprayed Y₂O₃ body having an OD of 305 mm, an ID of 301 mm, aheight of 102 mm and a wall thickness of 2 mm, that is, Y₂O₃ ceramiccrucible from which the carbon crucible had been removed.

Example 3

There was furnished a hollow carbon cylinder (CIP carbon substrate)having an OD of 300 mm, an ID of 294 mm, and a height of 100 mm. Theouter circumferential surface of the cylinder was roughened by shotblasting. Using a source powder of YF₃ and argon/hydrogen gas, plasmaspraying was carried out on the roughened surface. A sprayed YF₃ coatingwas deposited on the outer circumferential surface of the carboncylinder. Plasma spraying was terminated when the coating reached athickness of 2 mm.

The YF₃-coated carbon cylinder was placed in an oxidizing atmospherefurnace, where it was heated at 800° C. to burn out the carbon cylinder.With the furnace returned to room temperature, there was obtained ahollow cylinder-shape sprayed YF₃ body having an OD of 305 mm, an ID of301 mm, a height of 100 mm and a wall thickness of 2 mm, that is, YF₃ceramic cylinder from which the carbon cylinder had been removed.

Example 4

There was furnished a carbon crucible (carbon cup or CIP carbonsubstrate) having an OD of 300 mm, an ID of 294 mm, and a height of 100mm. The outer circumferential and bottom surfaces of the crucible wereroughened by shot blasting. Using a source powder of YF₃ andargon/hydrogen gas, plasma spraying was carried out on the roughenedsurface. A sprayed YF₃ coating was deposited on the outercircumferential and bottom surfaces of the carbon crucible. Plasmaspraying was terminated when the coating reached a thickness of 2 mm.

The YF₃-coated carbon crucible was placed in an oxidizing atmospherefurnace, where it was heated at 800° C. to burn out the carbon crucible.With the furnace returned to room temperature, there was obtained acup-shape sprayed YF₃ body having an OD of 305 mm, an ID of 301 mm, aheight of 102 mm and a wall thickness of 2 mm, that is, YF₃ ceramiccrucible from which the carbon crucible had been removed.

Example 5

There was furnished a carbon crucible (carbon cup or CIP carbonsubstrate) having an OD of 300 mm, an ID of 294 mm, and a height of 100mm. The outer circumferential and bottom surfaces of the crucible wereroughened by shot blasting. Using a source powder of tungsten (W) andargon/hydrogen gas, plasma spraying was carried out on the roughenedsurface. A sprayed W coating was deposited on the outer circumferentialand bottom surfaces of the carbon crucible. Plasma spraying wasterminated when the coating reached a thickness of 2 mm.

The W-coated carbon crucible was placed in an oxidizing atmospherefurnace, where it was heated at 800° C. to burn out the carbon crucible.With the furnace returned to room temperature, there was obtained acup-shape sprayed W body having an OD of 305 mm, an ID of 301 mm, aheight of 102 mm and a wall thickness of 2 mm, that is, W metal cruciblefrom which the carbon crucible had been removed.

Example 6

There was furnished a hollow carbon cylinder (CIP carbon substrate)having an OD of 300 mm, an ID of 294 mm, and a height of 100 mm. Theouter circumferential surface of the cylinder was roughened by shotblasting. Using a source powder of Y₂O₃ and argon/hydrogen gas, plasmaspraying was carried out on the roughened surface. A sprayed Y₂O₃coating was deposited on the outer circumferential surface of the carboncylinder. Plasma spraying was terminated when the coating reached athickness of 2 mm.

Another coating was deposited by plasma spraying using a source powderof yttrium aluminum garnet (YAG) and argon/hydrogen gas. A sprayed YAGcoating was deposited on the Y₂O₃ coating. Plasma spraying wasterminated when the YAG coating reached a thickness of 2 mm.

The (Y₂O₃+YAG)-coated carbon cylinder was placed in an oxidizingatmosphere furnace, where it was heated at 800° C. to burn out thecarbon cylinder. With the furnace returned to room temperature, therewas obtained a hollow cylinder-shape sprayed Y₂O₃+YAG body having an ODof 309 mm, an ID of 301 mm, a height of 100 mm and a wall thickness of 4mm, that is, Y₂O₃+YAG ceramic cylinder from which the carbon cylinderhad been removed.

Example 7

There was furnished a hollow carbon cylinder (CIP carbon substrate)having an OD of 300 mm, an ID of 294 mm, and a height of 100 mm. Theinner circumferential surface of the cylinder was roughened by shotblasting. Using a source powder of Y₂O₃ and argon/hydrogen gas, plasmaspraying was carried out on the roughened surface. A sprayed Y₂O₃coating was deposited on the inner surface of the carbon cylinder.Plasma spraying was terminated when the coating reached a thickness of 2mm.

The Y₂O₃-coated carbon cylinder was placed in an oxidizing atmospherefurnace, where it was heated at 800° C. to burn out the carbon cylinder.With the furnace returned to room temperature, there was obtained ahollow cylinder-shape sprayed Y₂O₃ body having an OD of 294 mm, an ID of290 mm, a height of 100 mm and a wall thickness of 2 mm, that is, Y₂O₃ceramic cylinder from which the carbon cylinder had been removed.

Example 8

There was furnished a hollow carbon cylinder (CIP carbon substrate)having an OD of 300 mm, an ID of 294 mm, and a height of 100 mm. Theinner circumferential surface of the cylinder was roughened by shotblasting. Using a source powder of Y₂O₃ and argon/hydrogen gas, plasmaspraying was carried out on the roughened surface. A sprayed Y₂O₃coating was deposited on the inner surface of the carbon cylinder.Plasma spraying was terminated when the coating reached a thickness of 2mm.

The carbon cylinder on the outside was machined by dry grinding. TheY₂O₃-coated carbon cylinder was placed in an oxidizing atmospherefurnace, where it was heated at 800° C. to burn out the remaining carboncylinder. With the furnace returned to room temperature, there wasobtained a hollow cylinder-shape sprayed Y₂O₃ body having an OD of 294mm, an ID of 290 mm, a height of 100 mm and a wall thickness of 2 mm,that is, Y₂O₃ ceramic cylinder from which the carbon cylinder had beenremoved.

Comparative Example 1

There was furnished a mold defining a cavity having an OD of 300 mm, anID of 294 mm, and a height of 100 mm. The mold cavity was filled withY₂O₃ source powder, which was press molded to form a compact having awall thickness of 3 mm. The compact cracked when it was released fromthe press mold, failing to obtain a molded Y₂O₃ body of cylindricalshape.

Comparative Example 2

There were furnished a neoprene rubber mold having a diameter of 300 mmand a height of 100 mm, a metal insert having a diameter of 290 mm and aheight of 100 mm, and a rubber lid. The mold cavity was filled with Y₂O₃source powder, which was molded under a hydraulic pressure of 2 ton/cm²using a cold isostatic pressing machine. There was obtained a moldedcompact having an OD of 296 mm, an ID of 290 mm and a height of 100 mm,with cylinder edges partially chipped away. The compact had a thin walland a low strength, and cracked when the metal insert was withdrawn,failing to obtain an acceptable molded part.

Comparative Example 3

There were furnished a neoprene rubber mold having a diameter of 300 mmand a height of 100 mm, a metal insert having a diameter of 250 mm and aheight of 100 mm, and a rubber lid. The mold cavity was filled with Y₂O₃source powder, which was molded under a hydraulic pressure of 2 ton/cm²using a cold isostatic pressing machine. There was obtained a moldedcompact having an OD of 290 mm, an ID of 250 mm and a height of 100 mm.The compact had a wall thickness of 20 mm.

Next, the compact was placed in an oxidizing atmosphere furnace where itwas fired at 1,700° C., obtaining a sintered body having an OD of 285mm, an ID of 245 mm, and a height of 95 mm.

Since the sintered body had a thick wall (20 mm), it was ground on itsouter surface until the wall thickness was reduced below 5 mm. Grindingrequired a long time until the OD was reduced to 255 mm. Cracksgenerated in the course of machining, indicating a high failure rate. Itwas difficult to obtain an acceptable Y₂O₃ ceramic body of cylindricalshape.

Japanese Patent Application No. 2013-211792 is incorporated herein byreference.

Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

1. A method for preparing a sprayed article, comprising the steps of:providing a carbon substrate of cylindrical shape having outer and innercircumferential surfaces, thermally spraying ceramic particles of a rareearth oxide and/or rare earth fluoride or metal particles of at leastone type selected from W, Mo and Ta, onto the outer or innercircumferential surface of the carbon substrate to form a sprayedcoating, and combustion treating the coated substrate to burn out thecarbon substrate, thus leaving the ceramic or metal-base sprayed coatingof cylindrical shape having a wall thickness of 0.5 to 5 mm.
 2. A methodfor preparing a sprayed article, comprising the steps of: providing acarbon substrate of cup shape having outer and inner circumferentialsurfaces and outer and inner bottom surfaces, thermally spraying ceramicparticles of a rare earth oxide and/or rare earth fluoride or metalparticles of at least one type selected from W, Mo and Ta, onto theouter circumferential and bottom surfaces or inner circumferential andbottom surfaces of the carbon substrate to form a sprayed coating, andcombustion treating the coated substrate to burn out the carbonsubstrate, thus leaving the ceramic or metal-base sprayed coating of cupshape having a wall thickness of 0.5 to 5 mm.
 3. The method of claim 1wherein only the step of combustion treating the coated substrate issufficient to burn out the carbon substrate.
 4. The method of claim 1,further comprising the step of machining the carbon substrate to reduceits wall thickness prior to the combustion treating step, and the stepof combustion treating the coated substrate is sufficient to burn outthe remaining carbon substrate.
 5. The method of claim 1 wherein thestep of combustion treating the coated substrate includes heating thecoated substrate at a temperature of 800° C. to 1,700° C. in anoxidizing atmosphere.
 6. The method of claim 1, further comprising thestep of roughening the surface of the carbon substrate to be sprayed,prior to the spraying step.
 7. The method of claim 1 wherein thespraying step includes alternately spraying ceramic particles ofdifferent rare earth oxides, or alternately spraying ceramic particlesof a rare earth oxide and ceramic particles of a rare earth fluoride toform the sprayed coating.
 8. The method of claim 1 wherein the carbonsubstrate has a round pipe shape.
 9. The method of claim 1 wherein thecarbon substrate is a CIP carbon substrate.
 10. The method of claim 1further comprising the step of additional thermal spraying ceramicparticles of a rare earth oxide and/or rare earth fluoride or metalparticles of at least one type selected from W, Mo and Ta, onto thesurface of the sprayed coating that has been in contact with the carbonsubstrate, thus correcting the deformation of the sprayed coating ofcylindrical shape after removal of the carbon substrate.
 11. The methodof claim 2 wherein only the step of combustion treating the coatedsubstrate is sufficient to burn out the carbon substrate.
 12. The methodof claim 2, further comprising the step of machining the carbonsubstrate to reduce its wall thickness prior to the combustion treatingstep, and the step of combustion treating the coated substrate issufficient to burn out the remaining carbon substrate.
 13. The method ofclaim 2 wherein the step of combustion treating the coated substrateincludes heating the coated substrate at a temperature of 800° C. to1,700° C. in an oxidizing atmosphere.
 14. The method of claim 2, furthercomprising the step of roughening the surface of the carbon substrate tobe sprayed, prior to the spraying step.
 15. The method of claim 2wherein the spraying step includes alternately spraying ceramicparticles of different rare earth oxides, or alternately sprayingceramic particles of a rare earth oxide and ceramic particles of a rareearth fluoride to form the sprayed coating.
 16. The method of claim 2wherein the carbon substrate has a round pipe shape.
 17. The method ofclaim 2 wherein the carbon substrate is a CIP carbon substrate.
 18. Themethod of claim 2 further comprising the step of additional thermalspraying ceramic particles of a rare earth oxide and/or rare earthfluoride or metal particles of at least one type selected from W, Mo andTa, onto the surface of the sprayed coating that has been in contactwith the carbon substrate, thus correcting the deformation of thesprayed coating of cup shape after removal of the carbon substrate.